# Supplementary Material (ESI) for Organic & Biomolecular Chemistry
# This journal is © The Royal Society of Chemistry 2003

data_global

_journal_coden_Cambridge         177

loop_
_publ_author_name
'Varinder Aggarwal'
'Harry Adams'
'Richard Grainger'
'Adrian D. Hobson'
'Gary K. Newton'
'Peter L. Spargo'

_publ_contact_author_name        'Prof Varinder Aggarwal'
_publ_contact_author_address     
;
Chemistry
Bristol University
Cantock's Close
Bristol
BS8 1TS
UNITED KINGDOM
;

_publ_contact_author_email       V.AGGARWAL@BRISTOL.AC.UK

_publ_requested_journal          'Organic & Biomolecular Chemistry'

_publ_section_title              
;
1,3-Dipolar cycloaddition reactions of
trans-2-methylene-1,3-dithiolane 1,3-dioxide with
3-oxidopyiridinium and 3-oxidopyrylium betaines: a highly
diastereoselective route to the tropane skeleton.
;

data_grange1
_database_code_CSD               206042

_audit_creation_method           SHELXL
_chemical_name_systematic        
; 
? 
;
_chemical_name_common            ?
_chemical_formula_moiety         ?
_chemical_formula_structural     ?
_chemical_formula_analytical     ?
_chemical_formula_sum            'C16 H17 N O3 S2'
_chemical_formula_weight         335.43
_chemical_melting_point          ?
_chemical_compound_source        ?

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Monoclinic
_symmetry_space_group_name_H-M   P2(1)/c

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'

_cell_length_a                   15.087(2)
_cell_length_b                   6.443(2)
_cell_length_c                   16.736(2)
_cell_angle_alpha                90.00
_cell_angle_beta                 106.840(10)
_cell_angle_gamma                90.00
_cell_volume                     1557.1(6)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    37
_cell_measurement_theta_min      9.662
_cell_measurement_theta_max      24.629

_exptl_crystal_description       ?
_exptl_crystal_colour            ?
_exptl_crystal_size_max          0.54
_exptl_crystal_size_mid          0.33
_exptl_crystal_size_min          0.28
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.431
_exptl_crystal_density_method    ?
_exptl_crystal_F_000             704
_exptl_absorpt_coefficient_mu    0.353
_exptl_absorpt_correction_type   ?
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?

_exptl_special_details           
; 
? 
;

_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device       'Siemens P4'
_diffrn_measurement_method       '\w scans'
_diffrn_standards_number         3
_diffrn_standards_interval_count 97
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        19.83
_diffrn_reflns_number            2748
_diffrn_reflns_av_R_equivalents  0.0449
_diffrn_reflns_av_sigmaI/netI    0.0406
_diffrn_reflns_limit_h_min       -1
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_k_min       -1
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_theta_min         2.53
_diffrn_reflns_theta_max         22.51
_reflns_number_total             2031
_reflns_number_observed          1660
_reflns_observed_criterion       >2sigma(I)

_computing_data_collection       'Siemens XSCANS'
_computing_cell_refinement       'Siemens XSCANS'
_computing_data_reduction        'Siemens XSCANS'
_computing_structure_solution    'SHELXS-86 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-93 (Sheldrick, 1993)'
_computing_molecular_graphics    'Siemens SHELXTL'
_computing_publication_material  'Siemens SHELXTL'

_refine_special_details          
; 
Refinement on F^2^ for ALL reflections except for 0 with very negative F^2^ 
or flagged by the user for potential systematic errors.  Weighted R-factors 
wR and all goodnesses of fit S are based on F^2^, conventional R-factors R 
are based on F, with F set to zero for negative F^2^. The observed criterion 
of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs etc. and is 
not relevant to the choice of reflections for refinement.  R-factors based 
on F^2^ are statistically about twice as large as those based on F, and R- 
factors based on ALL data will be even larger. 
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      
'calc w=1/[\s^2^(Fo^2^)+(0.0559P)^2^+0.6583P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    ?
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         2031
_refine_ls_number_parameters     199
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0538
_refine_ls_R_factor_obs          0.0418
_refine_ls_wR_factor_all         0.1117
_refine_ls_wR_factor_obs         0.1030
_refine_ls_goodness_of_fit_all   1.075
_refine_ls_goodness_of_fit_obs   1.109
_refine_ls_restrained_S_all      1.075
_refine_ls_restrained_S_obs      1.109
_refine_ls_shift/esd_max         0.000
_refine_ls_shift/esd_mean        0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_thermal_displace_type
_atom_site_occupancy
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_group
S1 S 0.31721(6) -0.34621(12) 0.58589(5) 0.0411(3) Uani 1 d . .
S3 S 0.37046(5) 0.10594(12) 0.56633(5) 0.0382(3) Uani 1 d . .
N8' N 0.2404(2) -0.1522(4) 0.71994(14) 0.0327(6) Uani 1 d . .
O1 O 0.2256(2) -0.3545(4) 0.5223(2) 0.0606(7) Uani 1 d . .
O3 O 0.4686(2) 0.1548(4) 0.61069(15) 0.0580(7) Uani 1 d . .
O2' O 0.3664(2) 0.1805(4) 0.88060(15) 0.0612(7) Uani 1 d . .
C2 C 0.3297(2) -0.0841(4) 0.6328(2) 0.0312(7) Uani 1 d . .
C4 C 0.3707(2) -0.0850(5) 0.4874(2) 0.0413(8) Uani 1 d . .
H4A H 0.4125(2) -0.0435(5) 0.4567(2) 0.080 Uiso 1 d R .
H4B H 0.3097(2) -0.0974(5) 0.4491(2) 0.080 Uiso 1 d R .
C5 C 0.4002(2) -0.2904(5) 0.5302(2) 0.0420(8) Uani 1 d . .
H5A H 0.3996(2) -0.3973(5) 0.4901(2) 0.080 Uiso 1 d R .
H5B H 0.4615(2) -0.2802(5) 0.5681(2) 0.080 Uiso 1 d R .
C7' C 0.3959(2) -0.1002(5) 0.7221(2) 0.0394(8) Uani 1 d . .
H7'A H 0.4388(2) 0.0134(5) 0.7341(2) 0.080 Uiso 1 d R .
H7'B H 0.4298(2) -0.2284(5) 0.7298(2) 0.080 Uiso 1 d R .
C1' C 0.3305(2) -0.0919(5) 0.7784(2) 0.0353(7) Uani 1 d . .
H1'A H 0.3493(2) -0.1872(5) 0.8243(2) 0.080 Uiso 1 d R .
C5' C 0.2361(2) -0.0217(5) 0.6469(2) 0.0314(7) Uani 1 d . .
H5'A H 0.1847(2) -0.0587(5) 0.6000(2) 0.080 Uiso 1 d R .
C4' C 0.2360(2) 0.2063(5) 0.6669(2) 0.0388(8) Uani 1 d . .
H4'A H 0.2055(2) 0.3021(5) 0.6238(2) 0.080 Uiso 1 d R .
C3' C 0.2786(2) 0.2761(5) 0.7437(2) 0.0442(8) Uani 1 d . .
H3'A H 0.2764(2) 0.4209(5) 0.7566(2) 0.080 Uiso 1 d R .
C2' C 0.3278(2) 0.1294(5) 0.8084(2) 0.0406(8) Uani 1 d . .
C9' C 0.1613(2) -0.1346(5) 0.7551(2) 0.0433(8) Uani 1 d . .
H9'A H 0.1611(2) 0.0010(5) 0.7787(2) 0.080 Uiso 1 d R .
H9'B H 0.1685(2) -0.2349(5) 0.7989(2) 0.080 Uiso 1 d R .
C10' C 0.0702(2) -0.1716(5) 0.6893(2) 0.0384(8) Uani 1 d . .
C11' C 0.0081(2) -0.0108(6) 0.6623(2) 0.0522(9) Uani 1 d . .
H11A H 0.0233(2) 0.1254(6) 0.6855(2) 0.080 Uiso 1 d R .
C12' C -0.0766(3) -0.0462(7) 0.6021(2) 0.0664(11) Uani 1 d . .
H12A H -0.1185(3) 0.0671(7) 0.5821(2) 0.080 Uiso 1 d R .
C13' C -0.0994(3) -0.2402(7) 0.5701(2) 0.0611(11) Uani 1 d . .
H13A H -0.1587(3) -0.2648(7) 0.5306(2) 0.080 Uiso 1 d R .
C14' C -0.0375(3) -0.3999(6) 0.5952(2) 0.0585(10) Uani 1 d . .
H14A H -0.0532(3) -0.5352(6) 0.5714(2) 0.080 Uiso 1 d R .
C15' C 0.0465(2) -0.3667(5) 0.6544(2) 0.0489(9) Uani 1 d . .
H15A H 0.0888(2) -0.4802(5) 0.6723(2) 0.080 Uiso 1 d R .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
S1 0.0470(5) 0.0295(5) 0.0507(5) -0.0023(4) 0.0204(4) -0.0030(4)
S3 0.0445(5) 0.0329(5) 0.0437(5) -0.0006(4) 0.0228(4) -0.0051(4)
N8' 0.0334(14) 0.0365(14) 0.0289(13) 0.0031(11) 0.0102(11) -0.0031(11)
O1 0.0460(14) 0.055(2) 0.079(2) -0.0255(13) 0.0149(13) -0.0155(12)
O3 0.0531(15) 0.068(2) 0.0583(15) -0.0182(13) 0.0241(12) -0.0311(13)
O2' 0.067(2) 0.065(2) 0.0423(14) -0.0158(12) 0.0013(12) -0.0102(13)
C2 0.030(2) 0.030(2) 0.035(2) 0.0011(13) 0.0123(13) -0.0011(13)
C4 0.049(2) 0.042(2) 0.037(2) -0.0050(15) 0.0186(15) -0.007(2)
C5 0.039(2) 0.047(2) 0.042(2) -0.009(2) 0.0159(15) 0.003(2)
C7' 0.031(2) 0.049(2) 0.038(2) 0.0025(15) 0.0085(14) 0.0040(15)
C1' 0.034(2) 0.040(2) 0.029(2) 0.0049(14) 0.0055(13) 0.0003(14)
C5' 0.029(2) 0.036(2) 0.0294(15) 0.0026(13) 0.0079(12) 0.0018(13)
C4' 0.040(2) 0.038(2) 0.043(2) 0.008(2) 0.020(2) 0.0092(15)
C3' 0.051(2) 0.035(2) 0.048(2) -0.005(2) 0.017(2) -0.003(2)
C2' 0.040(2) 0.046(2) 0.037(2) -0.006(2) 0.0117(15) -0.008(2)
C9' 0.042(2) 0.054(2) 0.039(2) 0.000(2) 0.0196(15) -0.007(2)
C10' 0.038(2) 0.044(2) 0.038(2) 0.0003(15) 0.0184(15) -0.007(2)
C11' 0.056(2) 0.047(2) 0.057(2) -0.009(2) 0.021(2) -0.002(2)
C12' 0.049(2) 0.073(3) 0.071(3) -0.004(2) 0.006(2) 0.012(2)
C13' 0.046(2) 0.083(3) 0.049(2) -0.009(2) 0.007(2) -0.010(2)
C14' 0.063(2) 0.054(2) 0.059(2) -0.016(2) 0.019(2) -0.018(2)
C15' 0.046(2) 0.044(2) 0.056(2) -0.004(2) 0.014(2) -0.002(2)

_geom_special_details            
; 
All esds (except the esd in the dihedral angle between two l.s. planes) 
are estimated using the full covariance matrix.  The cell esds are taken 
into account individually in the estimation of esds in distances, angles 
and torsion angles; correlations between esds in cell parameters are only 
used when they are defined by crystal symmetry.  An approximate (isotropic) 
treatment of cell esds is used for estimating esds involving l.s. planes. 
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
S1 O1 1.481(3) . ?
S1 C5 1.801(3) . ?
S1 C2 1.849(3) . ?
S3 O3 1.485(2) . ?
S3 C4 1.806(3) . ?
S3 C2 1.873(3) . ?
N8' C5' 1.469(4) . ?
N8' C1' 1.478(4) . ?
N8' C9' 1.479(4) . ?
O2' C2' 1.225(4) . ?
C2 C7' 1.542(4) . ?
C2 C5' 1.551(4) . ?
C4 C5 1.509(4) . ?
C7' C1' 1.549(4) . ?
C1' C2' 1.516(4) . ?
C5' C4' 1.507(4) . ?
C4' C3' 1.337(4) . ?
C3' C2' 1.467(5) . ?
C9' C10' 1.511(4) . ?
C10' C11' 1.382(5) . ?
C10' C15' 1.388(5) . ?
C11' C12' 1.398(5) . ?
C12' C13' 1.364(6) . ?
C13' C14' 1.371(6) . ?
C14' C15' 1.381(5) . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O1 S1 C5 106.21(15) . . ?
O1 S1 C2 107.31(13) . . ?
C5 S1 C2 92.07(14) . . ?
O3 S3 C4 107.31(15) . . ?
O3 S3 C2 107.02(14) . . ?
C4 S3 C2 93.40(14) . . ?
C5' N8' C1' 102.2(2) . . ?
C5' N8' C9' 116.1(2) . . ?
C1' N8' C9' 114.2(2) . . ?
C7' C2 C5' 103.4(2) . . ?
C7' C2 S1 107.9(2) . . ?
C5' C2 S1 108.4(2) . . ?
C7' C2 S3 112.9(2) . . ?
C5' C2 S3 113.0(2) . . ?
S1 C2 S3 110.85(14) . . ?
C5 C4 S3 108.2(2) . . ?
C4 C5 S1 105.5(2) . . ?
C2 C7' C1' 103.9(2) . . ?
N8' C1' C2' 111.0(2) . . ?
N8' C1' C7' 102.3(2) . . ?
C2' C1' C7' 108.5(3) . . ?
N8' C5' C4' 112.1(2) . . ?
N8' C5' C2 99.0(2) . . ?
C4' C5' C2 110.3(2) . . ?
C3' C4' C5' 120.7(3) . . ?
C4' C3' C2' 119.5(3) . . ?
O2' C2' C3' 123.3(3) . . ?
O2' C2' C1' 121.9(3) . . ?
C3' C2' C1' 114.7(3) . . ?
N8' C9' C10' 111.5(2) . . ?
C11' C10' C15' 118.3(3) . . ?
C11' C10' C9' 120.5(3) . . ?
C15' C10' C9' 121.2(3) . . ?
C10' C11' C12' 120.4(3) . . ?
C13' C12' C11' 120.4(4) . . ?
C12' C13' C14' 119.8(3) . . ?
C13' C14' C15' 120.4(4) . . ?
C14' C15' C10' 120.9(3) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
O1 S1 C2 C7' 153.1(2) . . . . ?
C5 S1 C2 C7' -99.2(2) . . . . ?
O1 S1 C2 C5' 41.7(2) . . . . ?
C5 S1 C2 C5' 149.4(2) . . . . ?
O1 S1 C2 S3 -82.9(2) . . . . ?
C5 S1 C2 S3 24.8(2) . . . . ?
O3 S3 C2 C7' 13.9(2) . . . . ?
C4 S3 C2 C7' 123.1(2) . . . . ?
O3 S3 C2 C5' 130.7(2) . . . . ?
C4 S3 C2 C5' -120.0(2) . . . . ?
O3 S3 C2 S1 -107.3(2) . . . . ?
C4 S3 C2 S1 1.9(2) . . . . ?
O3 S3 C4 C5 73.4(2) . . . . ?
C2 S3 C4 C5 -35.6(2) . . . . ?
S3 C4 C5 S1 58.8(2) . . . . ?
O1 S1 C5 C4 59.5(2) . . . . ?
C2 S1 C5 C4 -49.2(2) . . . . ?
C5' C2 C7' C1' 11.5(3) . . . . ?
S1 C2 C7' C1' -103.2(2) . . . . ?
S3 C2 C7' C1' 133.9(2) . . . . ?
C5' N8' C1' C2' 68.3(3) . . . . ?
C9' N8' C1' C2' -57.9(3) . . . . ?
C5' N8' C1' C7' -47.2(3) . . . . ?
C9' N8' C1' C7' -173.5(2) . . . . ?
C2 C7' C1' N8' 20.6(3) . . . . ?
C2 C7' C1' C2' -96.8(3) . . . . ?
C1' N8' C5' C4' -62.2(3) . . . . ?
C9' N8' C5' C4' 62.7(3) . . . . ?
C1' N8' C5' C2 54.0(2) . . . . ?
C9' N8' C5' C2 179.0(2) . . . . ?
C7' C2 C5' N8' -39.5(3) . . . . ?
S1 C2 C5' N8' 74.9(2) . . . . ?
S3 C2 C5' N8' -161.8(2) . . . . ?
C7' C2 C5' C4' 78.1(3) . . . . ?
S1 C2 C5' C4' -167.5(2) . . . . ?
S3 C2 C5' C4' -44.2(3) . . . . ?
N8' C5' C4' C3' 29.8(4) . . . . ?
C2 C5' C4' C3' -79.4(3) . . . . ?
C5' C4' C3' C2' 1.5(5) . . . . ?
C4' C3' C2' O2' -178.1(3) . . . . ?
C4' C3' C2' C1' 4.1(4) . . . . ?
N8' C1' C2' O2' 141.2(3) . . . . ?
C7' C1' C2' O2' -107.1(3) . . . . ?
N8' C1' C2' C3' -40.9(3) . . . . ?
C7' C1' C2' C3' 70.8(3) . . . . ?
C5' N8' C9' C10' 54.1(3) . . . . ?
C1' N8' C9' C10' 172.7(3) . . . . ?
N8' C9' C10' C11' -111.2(3) . . . . ?
N8' C9' C10' C15' 68.9(4) . . . . ?
C15' C10' C11' C12' 0.7(5) . . . . ?
C9' C10' C11' C12' -179.3(3) . . . . ?
C10' C11' C12' C13' 0.8(6) . . . . ?
C11' C12' C13' C14' -2.1(6) . . . . ?
C12' C13' C14' C15' 1.8(6) . . . . ?
C13' C14' C15' C10' -0.3(5) . . . . ?
C11' C10' C15' C14' -0.9(5) . . . . ?
C9' C10' C15' C14' 179.0(3) . . . . ?

_refine_diff_density_max         0.262
_refine_diff_density_min         -0.332
_refine_diff_density_rms         0.053